Coloration of synthetic polymeric material



United States Patent 2,911,314 COLORATION 0F SYNTHETIC POLYMERIC WilliamH. -Armento and Nikolaus Hebauf, Albany,

N.Y., assignors to, General Aniline 8z Film'Corporalion, New York, N.Y.,avcorporation of Delaware No Drawing. Application' December 17, 1954Serial No. 476,093

9 Claims. Cl. 106-168) This invention relates to. coloration ofsynthetic polymeric materialand more particularly to the use therefor ofdyestuffs of the formula cioNn-O-Qm \N OH R: I

i Nag wherein R and are-selected the group consisiting C 3 .QCH3, 2, a'SQ2N( C2H5)2\ It is an object ofthiS invention to provide syntl etici iThedye'stuifs of the above formula may be produced in wellknownmann'erby diazotiz ing an aromatic amineof the formula R 'and Rhavingthe valries given above, andco upling the diazotized compound with,2-hydroxy 3-carbazolecarboxylic acidf'p chloroanilideflof the formula Iotherwise known as-Naphthol ASLB.' Among the=aforementioned aromaticamines useful as diazo components in the production of the instantpigments, those wherein R is Cl in the 5-position and R is Cl, CH or OCHin the 2-position have been found to yield exceptional results in lightfastness properties, as indicated by resistance to change in shades whenexposed up to 117 hours in the 2,911,314 Patented Nov. 3, 1959Fadeometer. These preferred aromatic amines have the following formulae:

' QNH, 1

As examples of other aromatic amines which may be employed, there may bementioned 3- chloro-2-methy1- aniline, 4-chloro-2-methylaniline,2-nitro-4-methylaniline, 5-nitro-2-methoxyaniline, S-(N-diethylsulfamyl) -2-methxvamf i e n th Y The synthetic polymeric'tmaterialwhich maybe col l h ored in accordance with this invention may haveabasis of regenerated cellulose which may be made by the viscose orcuprammonium process, nitrocellulose, polyacrylonitrile, polymethacrylicacidand derivatives, polyvinyl chloride, polyvinyl acetate, polyvinylcyanide, polyethylene, polystyrene, polyesters such aspoly(ethyleneterephthalate), polyurethanes and polyamides such as nylon,or mixtures and copolymers thereof. Most advantageously, however, thesynthetic polymeric material may have a basis of an organicderivative ofcellulose such as an organic acid ester of cellulose or a celluloseether such as :c'ellulo'seacetate, "cellulose propionate, cellulosebutyrate, or mixed esters thereofi ethyl cellulose, benzylfcel lulose,and the like. 7

The preferred-mode of operation in accordancewith this inventioninvolves incorporation of the pigment into a solution of the syntheticpolymerie'material or into'ja hot melt thereof, inproportions rangingfrom about 0.5

to 3 percent or more by weight of the polymeric material dependent uponthe pa'rticular'material and dyestuff employed, the opacity and thedepth of shade desired and the like. The resulting solution orsuspension of pigment in synthetic polymeric material may then beemployed as a' coating composition or for the production of foils,films, filaments, fibers and other shaped objects colored in im'- provedlight fast brown shades, by extrusion, casting, molding, dipping,pouring ,or otherwise. shaping the, said solution or suspension. '7 i o'Alternatively, theinstant dyestuffs may be "mixed with a suitableorganic liquid (e.g. xylenes, banana oil, ethyl acetate, butyl acetate,and'the like, and mixtures thereof) and the resulting mixture may beemployed for coloring shaped products havinga basis of syntheticpolymeric ma: terial by contact'therewith as byimmersion, padding,spraying, spreading or the like. i 7 I When dispersed in organic solventsolutions or hot melts of synthetic polymeric. material preparatory tothe formation of coating for impregnating compositions or shaped coloredproducts therefrom, the dyestuffs of this invention are preferably addedin the form of asubstantially powder or slurry in an appropriate liquidsuch as used in cellulose acetate extrusion. However, in

some instances, particularly when coloring shaped products having abasis of synthetic polymeric material by treatment with solutions orsuspensions of the instant dyestulfs, or when the dyestulf is to bedispersed in an aqueas viscose or the like, admixture with the dyestiiffof 1.115 l to 50 or 60 percent by weight of a finely divided surfaceactive agent is desirable. V W W the production of a soft product inaddition to asslstlng in subsequent dispersing and coloring operations.As such surfactants, there may be mentioned polyoxyethylated higherfatty alcohols and acids, and other non-ionic polyoxyethylated surfaceactive agents derived from compounds containing a reactive hydrogenatom, sulfonates such as formaldehyde-naphthalene sulfonic acidcondensates, and the like.

The following examples, in which parts are by Weight unless otherwiseindicated are illustrative of the instant invention and are not to beregarded as limitative.

Example 1 15.75 g. 5-chloro-o-anisidifl was dissolved in 150 cc. waterand 30 cc. HCl 20 B'.) at 80 C. After cooling to C., 6.9 g. sodiumnitrite as a 31.5% solution was added. The diazo was stirred for onehour at about 0 C. to complete diazotization.

37 g. 2-hydroxy-3-earbazolecarboxylic acid p-chloroanilide was dissolvedin 100 cc. water and 1 0 glNaOI-I as a' 30% solution at- 60 C. This wasdiluted with 500 cci cold water. This was run into the cold diazosolution.-- The admixture was stirred well for 2' hours, after which 10cc. HCl (20 B.) was added and the eombi nation boiled for 1 hour,filtered, washed and dried. The resulting brown pigment has the apparentformula:

. -oH 01 t 1 H N=N 7 0H, Example 2 on the satin and Orlon base. Thesecoatings were ex:

posed in a standard Fadeometer for 117 hours andshowed practically nofading.

Example 3 A 50% dispersion of the pigment of Example l with Tamol L(sodium salt of sulfonated naphthalene form aldehyde condensate) iscombined with a viscose spinning solution or a cuprammonium spinningsolution in the necessary concentration to obtain a 0.5-3% (by weight offiber) dyeing, dependent on the shade desired, the solution spun and thefiber finished as usual. The re sulting brown regenerated cellulosefibers have excellent light fastness properties;

Example 4 30 parts dioctylphthalat'e (liquid plasticizer) and 120 partsof a copolymer of vinyl chloride, and vinyl acetate Such admixture aidsin are mixed in a Werner-Pfieiderer mixer for 1 hour dur* ing which timethe mass is' heated in order'to obtain a heavy viscous dope. The pigmentof Example 1 in the amount of ;5%, based on the weight of the copolymer,is milled in until a homogeneous mass is formed. It is run over a rollermill at 210'- Flftli'e'ri cured for 3 minutes at 290 F. to give a-browncolored plastic-film havingexcellent liglit-fastness properties Thisinvention has beendescribed with respect to cer taiijl prferreifjerfibod imff'ent's, and various modifications and 'variationsthereof willbe eomei obvious" to"- the person's l rilled the'ar'f.'Ieisto be linderstood that's'uch modifications andvaiiations are: to beincluded within the spirit and purview ofith'is' applicatimi and thescope of wherein R and R are selected from the group consistingot C1, CHOCH N0 and SO N(C H 2. A process for coloring fiber-forming syntheticorganic polymeric material comprising incorporating therein, inpreformed pigment form, a compound'of the for mula a wherein R and R areselected from the group consisting of Cl', CH OCH N0 and SO N(C H 3. Aprocess as defined in claim 2 wherein R is OCH and R is CI in the5-position.

4. Aprocess as defined in claim 2 wherein R is Cl and R is C1 in the5-position.

5. A process as defined in claim 2 wherein R is CH and R is C1 in the5-position.

6. A process as defined in claim 2 wherein the material has a basis ofcellulose acetate.

7. A process as defined in claim 2 wherein the material has a basis ofpolyacryl'onitrile.

8. A process as defined in claim 2 wherein the material has a basis of acopolymer' of vinyl chloride and vinyl acetate.

9. A process as defined in claim 2 wherein the mate rial has a basis ofregenerated cellulose.

References Cited in the file of this patent

1. A PROCESS FOR COLORING A FIBER-FORMING MATERIAL SELECTED FROM THEGROUP CONSISTING OF SYNTHETIC ORGANIC POLYMERIC MATERIAL, CELLULOSEESTERS, CELLULOSE ETHERS AND REGENERATED CELLULOSE COMPRISINGINCORPORATING THEREIN, IN PREFEROMED PIGMENT FORM, A COMPOUND OF THEFORMULA